EP0441391B1 - Method of forming three dimensional patterns - Google Patents
Method of forming three dimensional patterns Download PDFInfo
- Publication number
- EP0441391B1 EP0441391B1 EP91101761A EP91101761A EP0441391B1 EP 0441391 B1 EP0441391 B1 EP 0441391B1 EP 91101761 A EP91101761 A EP 91101761A EP 91101761 A EP91101761 A EP 91101761A EP 0441391 B1 EP0441391 B1 EP 0441391B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mold
- layer
- work surface
- forming
- pattern
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 35
- 239000000463 material Substances 0.000 claims description 49
- 239000010410 layer Substances 0.000 claims description 42
- -1 polyethylene Polymers 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 239000004567 concrete Substances 0.000 claims description 20
- 239000004925 Acrylic resin Substances 0.000 claims description 14
- 229920000178 Acrylic resin Polymers 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011241 protective layer Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000012615 aggregate Substances 0.000 description 17
- 239000000945 filler Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000012790 adhesive layer Substances 0.000 description 9
- 239000000123 paper Substances 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002344 surface layer Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012933 diacyl peroxide Substances 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 230000000873 masking effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- IONGEXNDPXANJD-UHFFFAOYSA-N 4-chloro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(Cl)C=C1 IONGEXNDPXANJD-UHFFFAOYSA-N 0.000 description 2
- ZTKDMNHEQMILPE-UHFFFAOYSA-N 4-methoxy-n,n-dimethylaniline Chemical compound COC1=CC=C(N(C)C)C=C1 ZTKDMNHEQMILPE-UHFFFAOYSA-N 0.000 description 2
- SJDILFZCXQHCRB-UHFFFAOYSA-N 4-tert-butyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(C(C)(C)C)C=C1 SJDILFZCXQHCRB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 2
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- KJOIQMXGNUKOLD-UHFFFAOYSA-N 1-[diacetyl(ethenyl)silyl]ethanone Chemical compound CC(=O)[Si](C=C)(C(C)=O)C(C)=O KJOIQMXGNUKOLD-UHFFFAOYSA-N 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- PJCNYQIIQZWBGS-UHFFFAOYSA-N 4-butyl-n,n-dimethylaniline Chemical compound CCCCC1=CC=C(N(C)C)C=C1 PJCNYQIIQZWBGS-UHFFFAOYSA-N 0.000 description 1
- SFAHTJULMBNOGW-UHFFFAOYSA-N 4-tert-butyl-n,n-diethylaniline Chemical compound CCN(CC)C1=CC=C(C(C)(C)C)C=C1 SFAHTJULMBNOGW-UHFFFAOYSA-N 0.000 description 1
- IYHIFXGFKVJNBB-UHFFFAOYSA-N 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonic acid Chemical compound C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S(O)(=O)=O IYHIFXGFKVJNBB-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VVAVKBBTPWYADW-UHFFFAOYSA-L Biebrich scarlet Chemical compound [Na+].[Na+].OC1=CC=C2C=CC=CC2=C1N=NC(C(=C1)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 VVAVKBBTPWYADW-UHFFFAOYSA-L 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000011384 asphalt concrete Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UHHXUPJJDHEMGX-UHFFFAOYSA-K azanium;manganese(3+);phosphonato phosphate Chemical compound [NH4+].[Mn+3].[O-]P([O-])(=O)OP([O-])([O-])=O UHHXUPJJDHEMGX-UHFFFAOYSA-K 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 229910001651 emery Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 0.000 description 1
- YQYUUNRAPYPAPC-UHFFFAOYSA-N n,n-diethyl-2-methylaniline Chemical compound CCN(CC)C1=CC=CC=C1C YQYUUNRAPYPAPC-UHFFFAOYSA-N 0.000 description 1
- XGSUIJYYBUZUDS-UHFFFAOYSA-N n,n-diethyl-4-methoxyaniline Chemical compound CCN(CC)C1=CC=C(OC)C=C1 XGSUIJYYBUZUDS-UHFFFAOYSA-N 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WOTPFVNWMLFMFW-ISLYRVAYSA-N para red Chemical compound OC1=CC=C2C=CC=CC2=C1\N=N\C1=CC=C(N(=O)=O)C=C1 WOTPFVNWMLFMFW-ISLYRVAYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- VVNRQZDDMYBBJY-UHFFFAOYSA-M sodium 1-[(1-sulfonaphthalen-2-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 VVNRQZDDMYBBJY-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Images
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F21/00—Implements for finishing work on buildings
- E04F21/02—Implements for finishing work on buildings for applying plasticised masses to surfaces, e.g. plastering walls
- E04F21/04—Patterns or templates; Jointing rulers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/10—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
- Y10S264/31—Processes of making tile and tile-like surfaces
Definitions
- This invention relates to a method of forming three-dimensional patterns. More particularly, this invention relates to a method of forming desired three-dimensional patterns on the surfaces of walls, floors, etc., molds for use in that methods for forming three-dimensional patterns, as well as a tool for removing the molds used in that method.
- method (a) the appearance of the final pattern is considerably damaged by burning the mold. Even if the mold is dissolved away with the aid of a solvent, solvent staining will occur.
- method (c) the mold in the joint can later be damaged or shed from the work surface.
- the releasable covering material has to be removed while the projection forming material remains incompletely hardened, so the unhardened projection forming material deposited on the surface of the covering material can drip in areas where projections are to be formed, which either damages the appearance of the finished pattern or presents difficulty in the pattern forming operation.
- method (b) requires two removing steps, one for removing the releasable covering material and the other for removing the mold, and this renders the overall operation cumbersome.
- a common problem to these conventional methods is that no special tool has been developed for use in removing the mold after the surfacing material hardens and the only tools available today are common screwdrivers with a thin wedge-shaped end and scrapers.
- the latter is inserted between the mold and the work surface and the mold is pried to be detached from the work surface.
- the screwdriver must be kept pushed during the operation but precise removal of the mold is difficult to achieve in this way.
- Scrapers are suitable for the purpose of removing burrs and other projections from the work surface but not suitable for removing the mold embedded in the surfacing material.
- EP-A-0 160 315 reveals a method of forming a decorative rugged surface pattern on a wall, a panel or the like, characterized in that a thick and soft main body of a molding frame having been adhered with a covering material which can be peeled off later on its top surface is stuck on an area to be processed, where the recessed surface of said pattern is to be formed, and after the spraying or trowelling material for forming protruding portion is applied, the covering material is removed together with a protrusion forming material laid on it, and said molding frame is removed in a later stage when the protrusion part material becomes dried and solidified.
- a first object, therefore, of the present invention is to provide a method by which three-dimensional patterns can be formed in a simple and easy-to-implement manner.
- a further object of the present invention is to provide a method using a mold that is capable of preventing the dripping of a surfacing material so as to facilitate pattern forming operation and produce a satisfactory finished surface and which therefore is suitable for the purpose of forming a desired three-dimensional pattern on the surface of a wall, floor, etc.
- a method which comprises attaching a pattern forming mold to the work surface where a desired pattern is to be formed, said pattern forming mold being formed from an expanded polyethylene, casting onto the work surface a surfacing material of an acrylic resin concrete composition, allowing the surfacing material to harden, and detaching and removing the pattern forming mold from the work surface.
- the acrylic resin concrete composition used as a surfacing material comprises:
- the pattern forming mold comprises a substrate layer made of an expanded polyethylene and at least one release layer formed as the topmost layer on the surface of said substrate layer.
- a rigid protective layer is provided between the release layer and the substrate layer.
- the area around the work surface on which a pattern is to be formed is masked.
- the same area is protected against staining by covering it with a sheet.
- Masking may be performed by attaching adhesive tape or a commercial polyethylene masking film.
- a polyethylene sheet may be used as an anti-stain sheet.
- a preliminary treatment is conducted to remove grease, foreign matter like mud and water, as well as any other dirt and deposits from the work surface.
- the preliminary treatment may be performed using a surface treating machine such as a scrabbling machine (e.g. LINAX®) or a demarcation line remover, and if the work surface is an asphalt paved surface, a polisher fitted with wire brushes may be used.
- a primer may be coated on the work surface in order to improve adhesion to an undercoat material and a joint filler that are described hereinafter.
- Useful primers include methyl methacrylate (MMA) or urethane modified MMA primers such as R41, R51B of Mitsui Petrochemical Industrial Products, Ltd.
- the coat weight is typically in the range of from about 100 to 500 g/m2.
- a pavement material may preliminarily be applied to make the work surface completely level.
- a suitable pavement material may be selected in accordance with the severity of surface flaws. If they are moderate, a resin mortar consisting of a resin composition comprising methyl methacrylate and a methacrylate polymer, mixed silica sand as an aggregate, as well as a pigment and a curing agent (e.g.R64SL of Mitsui Petrochemical Industrial Products, Ltd.) may be used.
- a resin concrete consisting of a resin composition comprising methyl methacrylate and a methacrylate polymer, gravel and silica sand as aggregates, and fillers such as calcium carbonate and a pigment (e.g. R17 of Mitsui Petrochemical Industrial Products, Ltd.) may be used.
- pavement materials can be applied to the work surface by ruling, raking or troweling.
- a joint filler for forming the joint of a brick pattern is applied as an undercoat to the level work surface.
- a joint filler is applied to provide a completely level coated surface so that good adhesion is insured between the work surface and a pattern forming mold which is to be attached thereto in a subsequent stage.
- a suitable joint filler may be selected in consideration of color contrast from the surface layer that is to be formed of a surfacing material to be discussed hereinafter which is made of an acrylic resin concrete composition.
- An illustrative example is a resin paste that comprises 5 - 15 parts by weight of an inorganic pigment as a colorant, 5 - 50 parts by weight of a filler such as talc, calcium carbonate or a silica sand powder, and 100 parts by weight of a resin composition chiefly made of methacrylic acid and a methyl methacrylate resin (e.g. Silical®R61 of Mitsui Petrochemical Industrial Products, Ltd.)
- the joint filler is typically coated in a thickness of about 0.1 - 2mm.
- marking is preferably conducted in order to insure that a pattern forming mold can be attached to an exact position on the work surface in the next step.
- longitudinal and transverse reference lines are preferably marked in an exact way.
- a mold 3 for forming a three-dimensional pattern (see Fig. 2) is attached to the hardened layer of joint filler 2 on top of the work surface 1 in accordance with the marked reference lines as shown in Fig. 1A.
- the mold 3 has an adhesive coated on its bottom surface 5 with which the mold is to be bonded to the hardened layer of joint filler 2.
- the adhesive is protected with release paper 6 that is applied to the bottom surface 5.
- the mold 3 is preferably formed of an expanded polyethylene having a blow ratio of ca. 3 - 7.
- An expanded polyethylene is used since it does not adhere to acrylic resin concrete and because it is not attacked by resin concrete.
- the thickness of the mold is not limited to any particular value and may be selected as appropriate for such factors as the shape and size of the pattern to be formed. As a guide figure, the range of ca. 1 - 2 mm may be adopted. If the particle size of the aggregate that is incorporated as a component of the acrylic resin concrete composition which is used as the surfacing material to be described hereinafter is to be taken in account, the thickness of the mold is preferably at least 3 - 4 times as much the maximum particle size of the aggregate, with the range of ca. 1 - 5 mm being mentioned as a guide figure.
- the mold 3 is preferably attached to the work surface in such a way that the two members adhere strongly to prevent lifting of the mold. If the surface of the hardened layer of joint filler 2 remains tuck, the mold 3 will sometimes fail to adhere strongly to the work surface. Hence, it is recommended that the work surface be examined and any defect such as tuck should be removed before the mold is attached.
- the surfacing material 7 is applied or cast to fill in the open spaces 8 in the mold as shown in Fig. 1B.
- An acrylic resin concrete composition is used as the surfacing material 7.
- the composition comprises:
- Examples of the monomer component (A) include: alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, methyl mathacrylate and ethyl methacrylate; as well as acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, 2,2-bis[4-(meth)acryloyloxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxycyclohexyl]propane, 2,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxyphenyl]propane, trimethylolpropane tri(meth)
- the polymer (B) may be exemplified by homo- or copolymers of the monomers listed above, in particular, (meth)acrylate esters.
- Examples of the aggregate (C) include silica sand, alumina, white Japanese marble (calcite), emery, ceramic sand and glass beads.
- these aggregates may be colored.
- Such colored aggregates may be prepared by forming a colored layer consisting of a silane coupling agent, a pigment and a binder component over all or part of the surfaces of aggregates. Pigments may be organic or inorganic.
- Exemplary organic pigments include Benzidine Yellow, Hansa Yellow, Lithol Red, alizarin lake, Pigment Scarlet 3B, Brilliant Carmine 6B, Permanent Red F-5R, Permanent Red 4R, Rhodamine B Lake, Rhodamine Y Lake, Lake Red C, Para Red, Peacock Blue Lake, Phthalocyanine Blue, Aniline Black, Permanent Yellow HR, PV Violet BL, quinacridone, perinone, anthraquinone, Chrome Phthal Yellow 6G, Chrome Phthal Yellow 3G and Chrome Phthal Yellow GR.
- Exemplary inorganic pigments include titanium oxide, zinc white, lithopone, white lead, cadmium yellow, chrome yellow, titanium yellow, zinc chromate, yellow ochre, chrome vermillion, vermillion, amber, yellow iron oxide, red iron oxide, cadmium red, red lead, prussian blue, ultramarine blue, cobalt blue, chromium oxide green, mineral violet, carbon black and iron black. While any of these organic and inorganic pigments can be used, suitable ones are selected as appropriate depending on the resin component of resin concrete.
- Suitable binder components include emulsions or solutions of resins such as epoxy, urethane and acrylic urethane resins.
- silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris ( ⁇ -methoxyethoxy)silane, vinyl triacetylsilane, and ⁇ -methacryloxypropyl trimethoxysilane.
- Other silane coupling agents that can be used include vinyl trichlorosilane, and ⁇ -[N- ⁇ -methacryloxyethyl)-N,N-dimethylammonium(chloride)]propyl trimethoxysilane.
- Colored aggregates can be prepared using the aggregate, pigment, binder component and silane coupling agent described above by permitting the silane coupling agent to be present during the coating of the colorant so that it is baked to the aggregate simultaneously.
- the aggregate (C) is incorporated in a proportion of ca. 1 - 6, preferably ca. 2 - 4, per unit volume of liquid.
- the acrylic resin concrete composition that comprises monomer component (A), polymer (B) and aggregate (C) may further contain a plasticizer (D) and a polymerizable unsaturated bond containing compound (E).
- a plasticizer (D) are phthalic acid esters including dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dipentyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate and butylbenzyl phthalate.
- Internal plasticizers can also be used as exemplified by ⁇ , ⁇ -unsaturated carboxylic acid esters that are copolymerizable with monomer component (A) and more specific examples are diethyl maleate, dibutyl maleate, dioctyl maleate, dibutyl fumarate and dioctyl fumarate.
- Examples of the polymerizable unsaturated bond containing compound (E) include: alkanediol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate and 1,4-butylene glycol di(meth)acrylate; and (meth)acrylic acid modified epoxy resins such as 2,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxyphenyl]propane, and commercial products available under the trade names "Ripoxy VR-60" and "Ripoxy VR-90" from Showa Highpolymer Co., Ltd.
- alkanediol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate and 1,4-butylene glycol di(meth)acrylate
- components (A), (B), (D) and (E) described above are to be used in combination, their respective proportions are such that monomer component (A) is 45 - 85 parts by weight, polymer (B) is 5 - 20 parts by weight and plasticizer (D) is 1 - 25 parts by weight, with (E) being the balance.
- the acrylic resin concrete composition can be hardened by incorporating a polymerization initiator together with the optional amine used as a cold curing accelerator.
- exemplary polymerization initiators include azo compounds and peroxides such as diacyl peroxides, alkyl peroxides, aralkyl peroxides, peracids and peracid esters, with diacyl peroxides being preferred.
- Exemplary diacyl peroxides include dibenzoyl peroxide, diacetyl peroxide, dicapryl peroxide, dilauroyl peroxide, and distearoyl peroxide.
- Amines may be primary, secondary or tertiary, with tertiary amines being used advantageously.
- Exemplary amines include aniline, toluidine, xylidine, phenylenediamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-di( ⁇ -hydroxyethyl)aniline, N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-dimethylanisidine, N,N-diethylanisidine, N,N-dimethyl-p-t-butylaniline, N,N-diethyl-p-t-butylaniline, N,N-dimethyl-p-chloroaniline, diphenylamine, and N,N-( ⁇ -hydroxyethyl)-p-toluidine Among these, tertiary amines having an electron donating substituent at least in the p-position of the benzene ring such as N,N-dimethyl-p-toluidine, N,N-dimethyl-
- the polymerization initiator and amines are generally used in such amounts that each is 0.1 - 20 parts by weight per 100 parts by weight of the sum of components (A), (B), (D) and (E).
- paraffins preferably paraffin waxes having melting points of 40 - 60°C are preferably added.
- paraffins are incorporated in amounts of 0.1 - 1.0 part by weight per 100 parts by weight of the sum of components (A), (B), (D) and (E).
- the surfacing material should be cast or applied to fill in the spaces in the mold immediately after the preparation of the acrylic resin concrete composition and in such a gentle way as to prevent the lifting of the mold from the work surface.
- troweling or some other techniques of application may be performed in conformity with the shape and other features of the work surface and the surface layer to be formed, with care being taken to minimize unwanted coverage of the mold with the surfacing material.
- the surfacing material is typically applied in a coat weight of ca. 4 kg/m2 if a surface layer 2 mm thick is to be formed.
- the applied surfacing material is then cured to harden.
- the curing time typically ranges from ca. 30 to 90 min, preferably ca. 40 - 60 min.
- the mold 3 is gently pulled up starting at one end, as shown in Fig. 1C, so that it is detached and removed from the work surface.
- the mold 3 is removed from the work surface immediately after the surfacing material has hardened in order to insure that the unhardened surfacing material on the mold will not drip to either foul or disfigure the finally produced pattern.
- a blade toll such as a scraper may be used to assist in the removal step. The operator is recommended to put on clean shoes or take any other precautions necessary to prevent the surface layer from being fouled during the removal of the mold.
- shedding of the surfacing material, burring of the joint and any other minor defects that can impair the appearance of the final pattern are preferably remedied.
- the surface layer and the joint over the work surface are thoroughly cleaned and provided with a uniform topcoat in order to prevent staining and give an appealing finish.
- Specific examples of the topcoat that can be applied include R81 Clear and R71 Clear of Mitsui Petrochemical Industrial Products, Ltd.
- the topcoat may be applied by various methods such as roller coating, brush coating or spray coating that may be properly selected depending upon the surface to be coated. Since the topcoat being applied is prone to collect in the joint, care should be taken to insure that the topcoat is evenly applied over the surface layer with standing topcoat being absorbed by a highly absorbent roller or brush.
- the applied topcoat is cured for ca. 30 min until it hardens completely. After the topcoat has hardened. the masking tape or film as well as the protective sheet are removed to complete the process of forming a desired three-dimensional pattern by the method of the present invention.
- Fig. 4 is a perspective view of the preferred mold which is generally indicated by 9 and which consists basically of a substrate layer 10 and a release layer 11 on its top. Below the substrate layer 10 is provided an adhesive layer 12 which permits the substrate layer 10 to be firmly adhered to the hardened layer of joint filler. When not in use, the adhesive layer 12 is preferably protected with release paper 13 that is applied to its underside. Release paper 13 has a release agent applied to those areas which correspond to the adhesive layer 12.
- the substrate layer 10 of the mold 9 is formed of an expanded polyethylene. It is particularly preferred that the substrate layer 10 is formed of an expanded polyethylene having a blow ratio of ca. 3 - 7 since it does not adhere to the acrylic resin concrete used as a surfacing material and because it is not attacked by resin concrete.
- the thickness of the substrate layer is not limited to any particular value and may be selected as appropriate for such factors as the shape and size of the pattern to be formed. As a guide figure, the range of ca. 1 - 2 mm may be adopted. If the particle size of the aggregate that is incorporated as a component of the acrylic resin concrete composition which is used as the surfacing material is to be taken into account, the thickness of the substrate layer is preferably at least 3 - 4 times as much as the maximum particle size of the aggregate, with the range of ca. 1 - 5 mm being mentioned as a guide figure.
- the mold 9 has at least one release layer 11 as the topmost layer on the substrate layer 10.
- the release layer 11 may be formed of any release agent that is releasable from the surfacing material used, and useful release agents include silicone rubber (in solvent) based compounds, wax (in solvent) based compounds and PVA based compounds. These release agents may be used either on their own or as admixtures and suitable compounds may be selected as appropriate for such factors as the material of the substrate layer.
- the release layer 11 may be formed by applying a suitable release agent to the surface of the substrate layer 10.
- An appropriate coating method may be selected from among known techniques including spray coating and brush coating.
- the adhesive layer 12 may be formed of any known adhesives including aliphatic petroleum resin (e.g. Hi-rez®), aromatic petroleum resin (e.g. Petrozin®) and petroleum resin (e.g. Tackace®).
- aliphatic petroleum resin e.g. Hi-rez®
- aromatic petroleum resin e.g. Petrozin®
- petroleum resin e.g. Tackace®
- the release paper 13 applied to the underside of the adhesive layer 12 comprises a release agent coated at least onto those surfaces which contact the substrate layer, and such release paper serves to protect the adhesive layer when it is not in use.
- the release paper 13 is separated as required and the exposed adhesive layer 12 is bonded to the work surface.
- the release paper 13 may be of any type that is commonly used in a class of applications as contemplated by the present invention and kraft paper may be mentioned as an example. Suitable release paper may be selected as appropriate for the adhesive agent of which the adhesive layer 12 is made.
- FIG. 6 Another example of the mold 9 is shown in Fig. 6, in which a rigid protective layer 14 is provided between the substrate layer 10 and the release layer 11 formed on top of the substrate layer 10. Since the protective layer 14 imparts appropriate rigidity to the substrate layer, the mold for forming a three-dimensional pattern can be attached to the hardened layer of joint filler with such high efficiency that even a mold having a large area can be handled without deformation. Hence the advantage of the mold having the construction shown in Fig. 6 (i.e., providing high operational efficiency) is enhanced as the area of the three-dimensional pattern to be formed increases.
- the rigid protective layer 14 may be made of paper or a synthetic resin such as polyethylene and it can be formed by bonding or thermally fusing a rigid sheet of kraft paper (120 »m) onto the top surface of the substrate layer with an adhesive layer 15 being interposed.
- the method of the present invention uses the method of the present invention to easily form three-dimensional patterns of various shapes on the surfaces of walls, floors, etc. If a mold having the construction shown in Fig. 2 is used in forming a three-dimensional pattern by this method, the following two advantages will result: the mold has a simple structure and hence can be fabricated at low cost; secondly, the method of forming a desired three-dimensional pattern can be practiced in a convenient manner.
- a mold having the construction shown in Fig. 4 which has at least two layers, i.e., a substrate layer and a release layer, the dripping of a surfacing material over the mold can be prevented so as to facilitate the pattern forming operation and produce a satisfactory finished surface.
- the mold is therefore suitable for the purpose of forming a desired three-dimensional pattern on the surface of a wall, floor, etc.
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Moulds, Cores, Or Mandrels (AREA)
- Laminated Bodies (AREA)
Description
- This invention relates to a method of forming three-dimensional patterns. More particularly, this invention relates to a method of forming desired three-dimensional patterns on the surfaces of walls, floors, etc., molds for use in that methods for forming three-dimensional patterns, as well as a tool for removing the molds used in that method.
- For the purpose of beautifying the asphalt concrete or cement concrete surfaces of floors or walls of buildings, platforms of railroad stations, concourses, pedestrian overpasses and pavements, the practice of forming brick or tile patterns or various other geometrical figures on those surfaces is gaining increasing acceptance these days. Also gaining wide acceptance is forming three-dimensional directional signs directly on walls, floors, etc.
- Three most common methods proposed so far for forming three-dimensional patterns or geometrical figures on walls, floors, road surfaces, etc. include:
- (a) a method comprising attaching an expanded polyethylene mold to the work surface, applying a projection forming material to fill in the mold, allowing the applied material to harden, and removing the mold by either burning or dissolving it away so as to form a pattern with intended projections and grooves (see Japanese Patent Publication No. 47593/1987);
- (b) a method comprising attaching a two-layered mold (having a releasable covering material on its top) to the work surface, applying a projection forming material to fill in the mold, removing the releasable covering material before the projection forming material solidifies or hardens and, after the projection forming material hardens completely, removing the mold to form a pattern with intended projections and grooves [see Japanese Patent Application (kokai) No. 233264/1985]; and
- (c) a method which is the same as method (b) except that the mold remaining after the releasable covering material is removed is left intact as a joint filler on the work surface [see Japanese Patent Application (kokai) No. 111062/1987].
- The three methods described above have their own defects. In method (a), the appearance of the final pattern is considerably damaged by burning the mold. Even if the mold is dissolved away with the aid of a solvent, solvent staining will occur. In method (c), the mold in the joint can later be damaged or shed from the work surface. In both methods (b) and (c), the releasable covering material has to be removed while the projection forming material remains incompletely hardened, so the unhardened projection forming material deposited on the surface of the covering material can drip in areas where projections are to be formed, which either damages the appearance of the finished pattern or presents difficulty in the pattern forming operation. Further, method (b) requires two removing steps, one for removing the releasable covering material and the other for removing the mold, and this renders the overall operation cumbersome.
- A common problem to these conventional methods is that no special tool has been developed for use in removing the mold after the surfacing material hardens and the only tools available today are common screwdrivers with a thin wedge-shaped end and scrapers. However, it has not been easy to remove the mold with conventional screwdrivers or scrapers. For instance, in order to remove the mold with a conventional screwdriver, the latter is inserted between the mold and the work surface and the mold is pried to be detached from the work surface. Further, the screwdriver must be kept pushed during the operation but precise removal of the mold is difficult to achieve in this way. Scrapers are suitable for the purpose of removing burrs and other projections from the work surface but not suitable for removing the mold embedded in the surfacing material.
- EP-A-0 160 315 reveals a method of forming a decorative rugged surface pattern on a wall, a panel or the like, characterized in that a thick and soft main body of a molding frame having been adhered with a covering material which can be peeled off later on its top surface is stuck on an area to be processed, where the recessed surface of said pattern is to be formed, and after the spraying or trowelling material for forming protruding portion is applied, the covering material is removed together with a protrusion forming material laid on it, and said molding frame is removed in a later stage when the protrusion part material becomes dried and solidified.
- A first object, therefore, of the present invention is to provide a method by which three-dimensional patterns can be formed in a simple and easy-to-implement manner.
- A further object of the present invention is to provide a method using a mold that is capable of preventing the dripping of a surfacing material so as to facilitate pattern forming operation and produce a satisfactory finished surface and which therefore is suitable for the purpose of forming a desired three-dimensional pattern on the surface of a wall, floor, etc.
- The above objects of the present invention can be attained by a method which comprises attaching a pattern forming mold to the work surface where a desired pattern is to be formed, said pattern forming mold being formed from an expanded polyethylene, casting onto the work surface a surfacing material of an acrylic resin concrete composition, allowing the surfacing material to harden, and detaching and removing the pattern forming mold from the work surface.
- The acrylic resin concrete composition used as a surfacing material comprises:
- (A) at least one monomer component selected from among (meth)acrylic acid and esters thereof, in an amount of 45-85 parts by weight;
- (B) a polymer that can dissolve in said monomer component (A) or that is swollen by said monomer component (A), in an amount of 5-20 parts by weight; and
- (C) an aggregate in a proportion of 1-6 times the amount of (A) + (B) by volume.
- In a preferred embodiment of the present invention the pattern forming mold comprises a substrate layer made of an expanded polyethylene and at least one release layer formed as the topmost layer on the surface of said substrate layer.
- Preferably, a rigid protective layer is provided between the release layer and the substrate layer.
- Fig. 1 shows the major steps of forming a three-dimensional pattern by the method of the present invention;
- Fig. 2 shows an example of the mold which is used in forming a three-dimensional pattern by said method;
- Fig. 3 is a partial enlarged cross-sectional view of said mold;
- Fig. 4 is a perspective view showing a preferred example of the mold for use in forming a three-dimensional pattern by the method of the present invention;
- Fig. 5 is a cross section that shows schematically the mold of Fig. 4;
- Fig. 6 is a cross section showing schematically a more preferred example of the mold.
- The method of the present invention for forming three-dimensional patterns on flat surfaces such as those of pavements and walls is described below in detail with reference to Figs. 1A - 1D.
- First, the area around the work surface on which a pattern is to be formed is masked. Preferably, the same area is protected against staining by covering it with a sheet. Masking may be performed by attaching adhesive tape or a commercial polyethylene masking film. A polyethylene sheet may be used as an anti-stain sheet.
- In the next step, a preliminary treatment is conducted to remove grease, foreign matter like mud and water, as well as any other dirt and deposits from the work surface. When the work surface is a cement concrete or cement mortar paved surface, the preliminary treatment may be performed using a surface treating machine such as a scrabbling machine (e.g. LINAX®) or a demarcation line remover, and if the work surface is an asphalt paved surface, a polisher fitted with wire brushes may be used.
- If necessary, a primer may be coated on the work surface in order to improve adhesion to an undercoat material and a joint filler that are described hereinafter. Useful primers include methyl methacrylate (MMA) or urethane modified MMA primers such as R41, R51B of Mitsui Petrochemical Industrial Products, Ltd.
- When primers are to be coated on the work surface, the coat weight is typically in the range of from about 100 to 500 g/m².
- If the work surface has steps, roughness, cracks and other surface flaws, a pavement material may preliminarily be applied to make the work surface completely level. A suitable pavement material may be selected in accordance with the severity of surface flaws. If they are moderate, a resin mortar consisting of a resin composition comprising methyl methacrylate and a methacrylate polymer, mixed silica sand as an aggregate, as well as a pigment and a curing agent (e.g.R64SL of Mitsui Petrochemical Industrial Products, Ltd.) may be used. If surface flaws are severe, a resin concrete consisting of a resin composition comprising methyl methacrylate and a methacrylate polymer, gravel and silica sand as aggregates, and fillers such as calcium carbonate and a pigment (e.g. R17 of Mitsui Petrochemical Industrial Products, Ltd.) may be used.
- These pavement materials can be applied to the work surface by ruling, raking or troweling.
- In the next step, a joint filler for forming the joint of a brick pattern is applied as an undercoat to the level work surface. A joint filler is applied to provide a completely level coated surface so that good adhesion is insured between the work surface and a pattern forming mold which is to be attached thereto in a subsequent stage. A suitable joint filler may be selected in consideration of color contrast from the surface layer that is to be formed of a surfacing material to be discussed hereinafter which is made of an acrylic resin concrete composition. An illustrative example is a resin paste that comprises 5 - 15 parts by weight of an inorganic pigment as a colorant, 5 - 50 parts by weight of a filler such as talc, calcium carbonate or a silica sand powder, and 100 parts by weight of a resin composition chiefly made of methacrylic acid and a methyl methacrylate resin (e.g. Silical®R61 of Mitsui Petrochemical Industrial Products, Ltd.)
- The joint filler is typically coated in a thickness of about 0.1 - 2mm.
- After the joint filler hardens, marking is preferably conducted in order to insure that a pattern forming mold can be attached to an exact position on the work surface in the next step. In this case, longitudinal and transverse reference lines are preferably marked in an exact way.
- After the preliminary treatments described above, a
mold 3 for forming a three-dimensional pattern (see Fig. 2) is attached to the hardened layer ofjoint filler 2 on top of thework surface 1 in accordance with the marked reference lines as shown in Fig. 1A. - As shown in Figs. 2 and 3, the
mold 3 has an adhesive coated on itsbottom surface 5 with which the mold is to be bonded to the hardened layer ofjoint filler 2. When not in use, the adhesive is protected withrelease paper 6 that is applied to thebottom surface 5. - The
mold 3 is preferably formed of an expanded polyethylene having a blow ratio of ca. 3 - 7. An expanded polyethylene is used since it does not adhere to acrylic resin concrete and because it is not attacked by resin concrete. - The thickness of the mold is not limited to any particular value and may be selected as appropriate for such factors as the shape and size of the pattern to be formed. As a guide figure, the range of ca. 1 - 2 mm may be adopted. If the particle size of the aggregate that is incorporated as a component of the acrylic resin concrete composition which is used as the surfacing material to be described hereinafter is to be taken in account, the thickness of the mold is preferably at least 3 - 4 times as much the maximum particle size of the aggregate, with the range of ca. 1 - 5 mm being mentioned as a guide figure.
- The
mold 3 is preferably attached to the work surface in such a way that the two members adhere strongly to prevent lifting of the mold. If the surface of the hardened layer ofjoint filler 2 remains tuck, themold 3 will sometimes fail to adhere strongly to the work surface. Hence, it is recommended that the work surface be examined and any defect such as tuck should be removed before the mold is attached. - After the
mold 3 is attached to the work surface in the manner described above, the surfacing material 7 is applied or cast to fill in theopen spaces 8 in the mold as shown in Fig. 1B. - An acrylic resin concrete composition is used as the surfacing material 7. The composition comprises:
- (A) at least one monomer component selected from among (meth) acrylic acid and ester compounds thereof;
- (B) a polymer that can dissolve in said monomer component (A) or that is swollen by said monomer component; and
- (C) an aggregate.
- Examples of the monomer component (A) include: alkyl (meth)acrylates such as methyl acrylate, ethyl acrylate, methyl mathacrylate and ethyl methacrylate; as well as acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, 2,2-bis[4-(meth)acryloyloxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxycyclohexyl]propane, 2,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxyphenyl]propane, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. These compounds may be used either on their own or as admixtures.
- The polymer (B) may be exemplified by homo- or copolymers of the monomers listed above, in particular, (meth)acrylate esters.
- Examples of the aggregate (C) include silica sand, alumina, white Japanese marble (calcite), emery, ceramic sand and glass beads. In order to produce a colored surface layer, these aggregates may be colored. Such colored aggregates may be prepared by forming a colored layer consisting of a silane coupling agent, a pigment and a binder component over all or part of the surfaces of aggregates. Pigments may be organic or inorganic. Exemplary organic pigments include Benzidine Yellow, Hansa Yellow, Lithol Red, alizarin lake, Pigment Scarlet 3B, Brilliant Carmine 6B, Permanent Red F-5R, Permanent Red 4R, Rhodamine B Lake, Rhodamine Y Lake, Lake Red C, Para Red, Peacock Blue Lake, Phthalocyanine Blue, Aniline Black, Permanent Yellow HR, PV Violet BL, quinacridone, perinone, anthraquinone, Chrome Phthal Yellow 6G, Chrome Phthal Yellow 3G and Chrome Phthal Yellow GR. Exemplary inorganic pigments include titanium oxide, zinc white, lithopone, white lead, cadmium yellow, chrome yellow, titanium yellow, zinc chromate, yellow ochre, chrome vermillion, vermillion, amber, yellow iron oxide, red iron oxide, cadmium red, red lead, prussian blue, ultramarine blue, cobalt blue, chromium oxide green, mineral violet, carbon black and iron black. While any of these organic and inorganic pigments can be used, suitable ones are selected as appropriate depending on the resin component of resin concrete.
- Suitable binder components include emulsions or solutions of resins such as epoxy, urethane and acrylic urethane resins.
- Preferred examples of silane coupling agents include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (β-methoxyethoxy)silane, vinyl triacetylsilane, and γ-methacryloxypropyl trimethoxysilane. Other silane coupling agents that can be used include vinyl trichlorosilane, and γ-[N-β-methacryloxyethyl)-N,N-dimethylammonium(chloride)]propyl trimethoxysilane.
- Colored aggregates can be prepared using the aggregate, pigment, binder component and silane coupling agent described above by permitting the silane coupling agent to be present during the coating of the colorant so that it is baked to the aggregate simultaneously.
- The aggregate (C) is incorporated in a proportion of ca. 1 - 6, preferably ca. 2 - 4, per unit volume of liquid.
- The acrylic resin concrete composition that comprises monomer component (A), polymer (B) and aggregate (C) may further contain a plasticizer (D) and a polymerizable unsaturated bond containing compound (E). Exemplary plasticizers (D) are phthalic acid esters including dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dipentyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate and butylbenzyl phthalate. Internal plasticizers can also be used as exemplified by α, β-unsaturated carboxylic acid esters that are copolymerizable with monomer component (A) and more specific examples are diethyl maleate, dibutyl maleate, dioctyl maleate, dibutyl fumarate and dioctyl fumarate.
- Examples of the polymerizable unsaturated bond containing compound (E) include: alkanediol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate and 1,4-butylene glycol di(meth)acrylate; and (meth)acrylic acid modified epoxy resins such as 2,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxyphenyl]propane, and commercial products available under the trade names "Ripoxy VR-60" and "Ripoxy VR-90" from Showa Highpolymer Co., Ltd.
- If components (A), (B), (D) and (E) described above are to be used in combination, their respective proportions are such that monomer component (A) is 45 - 85 parts by weight, polymer (B) is 5 - 20 parts by weight and plasticizer (D) is 1 - 25 parts by weight, with (E) being the balance.
- The acrylic resin concrete composition can be hardened by incorporating a polymerization initiator together with the optional amine used as a cold curing accelerator. Exemplary polymerization initiators include azo compounds and peroxides such as diacyl peroxides, alkyl peroxides, aralkyl peroxides, peracids and peracid esters, with diacyl peroxides being preferred. Exemplary diacyl peroxides include dibenzoyl peroxide, diacetyl peroxide, dicapryl peroxide, dilauroyl peroxide, and distearoyl peroxide. Amines may be primary, secondary or tertiary, with tertiary amines being used advantageously. Exemplary amines include aniline, toluidine, xylidine, phenylenediamine, N,N-dimethylaniline, N,N-diethylaniline, N,N-di(β-hydroxyethyl)aniline, N,N-dimethyltoluidine, N,N-diethyltoluidine, N,N-dimethylanisidine, N,N-diethylanisidine, N,N-dimethyl-p-t-butylaniline, N,N-diethyl-p-t-butylaniline, N,N-dimethyl-p-chloroaniline, diphenylamine, and N,N-(β-hydroxyethyl)-p-toluidine Among these, tertiary amines having an electron donating substituent at least in the p-position of the benzene ring such as N,N-dimethyl-p-toluidine, N,N-dimethyl-p-butylaniline, N,N-dimethylanisidine, N,N-dimethyl-p-chloroaniline and N,N-bis(β-hydroxyethyl)-p-toluidine are preferred, with N,N-dimethyl-p-toluidine and N,N-dimethyl-p-t-butylaniline being particularly preferred.
- The polymerization initiator and amines are generally used in such amounts that each is 0.1 - 20 parts by weight per 100 parts by weight of the sum of components (A), (B), (D) and (E).
- In order to prevent insufficient progress of a surface hardening reaction due to the trapping of radicals by aerial oxygen, solid paraffins, preferably paraffin waxes having melting points of 40 - 60°C are preferably added. Such paraffins are incorporated in amounts of 0.1 - 1.0 part by weight per 100 parts by weight of the sum of components (A), (B), (D) and (E).
- The surfacing material should be cast or applied to fill in the spaces in the mold immediately after the preparation of the acrylic resin concrete composition and in such a gentle way as to prevent the lifting of the mold from the work surface. To this end , troweling or some other techniques of application may be performed in conformity with the shape and other features of the work surface and the surface layer to be formed, with care being taken to minimize unwanted coverage of the mold with the surfacing material.
- The surfacing material is typically applied in a coat weight of ca. 4 kg/m² if a
surface layer 2 mm thick is to be formed. - The applied surfacing material is then cured to harden. The curing time typically ranges from ca. 30 to 90 min, preferably ca. 40 - 60 min.
- After the surfacing material hardens, the
mold 3 is gently pulled up starting at one end, as shown in Fig. 1C, so that it is detached and removed from the work surface. Preferably, themold 3 is removed from the work surface immediately after the surfacing material has hardened in order to insure that the unhardened surfacing material on the mold will not drip to either foul or disfigure the finally produced pattern. If extensive coverage with the surfacing material makes it difficult to remove themold 3 efficiently, a blade toll such as a scraper may be used to assist in the removal step. The operator is recommended to put on clean shoes or take any other precautions necessary to prevent the surface layer from being fouled during the removal of the mold. After the mold removal is completed, shedding of the surfacing material, burring of the joint and any other minor defects that can impair the appearance of the final pattern are preferably remedied. - The above-described steps lead to the formation of a brick patterned surface layer over the
work surface 1 as shown in Fig 1D. - After removing the mold, the surface layer and the joint over the work surface are thoroughly cleaned and provided with a uniform topcoat in order to prevent staining and give an appealing finish. Specific examples of the topcoat that can be applied include R81 Clear and R71 Clear of Mitsui Petrochemical Industrial Products, Ltd. The topcoat may be applied by various methods such as roller coating, brush coating or spray coating that may be properly selected depending upon the surface to be coated. Since the topcoat being applied is prone to collect in the joint, care should be taken to insure that the topcoat is evenly applied over the surface layer with standing topcoat being absorbed by a highly absorbent roller or brush.
- The applied topcoat is cured for ca. 30 min until it hardens completely. After the topcoat has hardened. the masking tape or film as well as the protective sheet are removed to complete the process of forming a desired three-dimensional pattern by the method of the present invention.
- The foregoing description concerns an embodiment in which a three-dimensional pattern is formed using a single-layered mold. A preferred example of the mold is described below with reference to Figs. 4 and 5. Fig. 4 is a perspective view of the preferred mold which is generally indicated by 9 and which consists basically of a
substrate layer 10 and arelease layer 11 on its top. Below thesubstrate layer 10 is provided anadhesive layer 12 which permits thesubstrate layer 10 to be firmly adhered to the hardened layer of joint filler. When not in use, theadhesive layer 12 is preferably protected withrelease paper 13 that is applied to its underside.Release paper 13 has a release agent applied to those areas which correspond to theadhesive layer 12. - The
substrate layer 10 of themold 9 is formed of an expanded polyethylene. It is particularly preferred that thesubstrate layer 10 is formed of an expanded polyethylene having a blow ratio of ca. 3 - 7 since it does not adhere to the acrylic resin concrete used as a surfacing material and because it is not attacked by resin concrete. - The thickness of the substrate layer is not limited to any particular value and may be selected as appropriate for such factors as the shape and size of the pattern to be formed. As a guide figure, the range of ca. 1 - 2 mm may be adopted. If the particle size of the aggregate that is incorporated as a component of the acrylic resin concrete composition which is used as the surfacing material is to be taken into account, the thickness of the substrate layer is preferably at least 3 - 4 times as much as the maximum particle size of the aggregate, with the range of ca. 1 - 5 mm being mentioned as a guide figure.
- The
mold 9 has at least onerelease layer 11 as the topmost layer on thesubstrate layer 10. Therelease layer 11 may be formed of any release agent that is releasable from the surfacing material used, and useful release agents include silicone rubber (in solvent) based compounds, wax (in solvent) based compounds and PVA based compounds. These release agents may be used either on their own or as admixtures and suitable compounds may be selected as appropriate for such factors as the material of the substrate layer. - The
release layer 11 may be formed by applying a suitable release agent to the surface of thesubstrate layer 10. An appropriate coating method may be selected from among known techniques including spray coating and brush coating. - The
adhesive layer 12 may be formed of any known adhesives including aliphatic petroleum resin (e.g. Hi-rez®), aromatic petroleum resin (e.g. Petrozin®) and petroleum resin (e.g. Tackace®). - The
release paper 13 applied to the underside of theadhesive layer 12 comprises a release agent coated at least onto those surfaces which contact the substrate layer, and such release paper serves to protect the adhesive layer when it is not in use. Therelease paper 13 is separated as required and the exposedadhesive layer 12 is bonded to the work surface. Therelease paper 13 may be of any type that is commonly used in a class of applications as contemplated by the present invention and kraft paper may be mentioned as an example. Suitable release paper may be selected as appropriate for the adhesive agent of which theadhesive layer 12 is made. - Another example of the
mold 9 is shown in Fig. 6, in which a rigidprotective layer 14 is provided between thesubstrate layer 10 and therelease layer 11 formed on top of thesubstrate layer 10. Since theprotective layer 14 imparts appropriate rigidity to the substrate layer, the mold for forming a three-dimensional pattern can be attached to the hardened layer of joint filler with such high efficiency that even a mold having a large area can be handled without deformation. Hence the advantage of the mold having the construction shown in Fig. 6 (i.e., providing high operational efficiency) is enhanced as the area of the three-dimensional pattern to be formed increases. - The rigid
protective layer 14 may be made of paper or a synthetic resin such as polyethylene and it can be formed by bonding or thermally fusing a rigid sheet of kraft paper (120 »m) onto the top surface of the substrate layer with anadhesive layer 15 being interposed. - While the method of the present invention has been described above in relation to the formation of a brick-shaped three-dimensional pattern on a flat surface, it should be noted that this is not the sole case for the applicability of the present invention and that it is also applicable to the formation of three-dimensional patterns in other situations such as tile facing, stone masonry and natural stone setting. It should also be noted that the shape of three-dimensional patterns that can be formed by the present invention are in no way limited to brick-shaped patterns and three-dimensional patterns of any other shapes can be formed using molds having corresponding shapes including those of animals, plants, designed pictures of scenery, characters, symbolic marks and numerals.
- Using the method of the present invention, three-dimensional patterns of various shapes can be easily formed on the surfaces of walls, floors, etc. If a mold having the construction shown in Fig. 2 is used in forming a three-dimensional pattern by this method, the following two advantages will result: the mold has a simple structure and hence can be fabricated at low cost; secondly, the method of forming a desired three-dimensional pattern can be practiced in a convenient manner.
- Further, by using a mold having the construction shown in Fig. 4 which has at least two layers, i.e., a substrate layer and a release layer, the dripping of a surfacing material over the mold can be prevented so as to facilitate the pattern forming operation and produce a satisfactory finished surface. The mold is therefore suitable for the purpose of forming a desired three-dimensional pattern on the surface of a wall, floor, etc.
Claims (3)
- A method of forming a three-dimensional pattern from an acrylic resin concrete composition which comprises:
attaching a pattern forming mold (3) to a work surface (1) where a three-dimensional pattern is to be formed, said pattern forming mold (3) being formed from an expanded polyethylene;
casting onto said work surface (1) a surfacing material (7) of an acrylic resin concrete composition comprising:(A) at least one monomer compound selected from the group consisting of acrylic acid, methacrylic acid and esters thereof, in an amount of 45-85 parts by weight,(B) a polymer that dissolves in said monomer component (A) or that is swollen by said monomer component (A), in an amount of 5-20 parts by weight, and(C) an aggregate in a proportion of 1-6 times the amount of (A) + (B) by volume;allowing said acrylic resin concrete composition of said surfacing material (7) to harden; and then
detaching and removing said pattern forming mold (3) from said work surface (1) and said hardened surfacing material (7). - The method according to claim 1, wherein said pattern forming mold (9) comprises a substrate layer (10) made of an expanded polyethylene and at least one release layer (11) formed as the topmost layer on the surface of said substrate layer (10).
- The method according to claim 2, wherein a rigid protective layer (14) is provided between said release layer (11) and said substrate layer (10).
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29976/90 | 1990-02-09 | ||
JP2029976A JP2790354B2 (en) | 1990-02-09 | 1990-02-09 | Three-dimensional pattern forming method |
JP89861/90 | 1990-08-28 | ||
JP8986190U JPH0752875Y2 (en) | 1990-08-28 | 1990-08-28 | Form removal jig |
JP29422790A JPH04169657A (en) | 1990-10-31 | 1990-10-31 | Solid pattern formwork and solid pattern forming method using same formwork |
JP294227/90 | 1990-10-31 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0441391A2 EP0441391A2 (en) | 1991-08-14 |
EP0441391A3 EP0441391A3 (en) | 1992-08-12 |
EP0441391B1 true EP0441391B1 (en) | 1995-01-18 |
Family
ID=27286795
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91101761A Expired - Lifetime EP0441391B1 (en) | 1990-02-09 | 1991-02-08 | Method of forming three dimensional patterns |
Country Status (5)
Country | Link |
---|---|
US (1) | US5169573A (en) |
EP (1) | EP0441391B1 (en) |
DE (1) | DE69106731T2 (en) |
DK (1) | DK0441391T3 (en) |
NO (1) | NO179419C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19908235C2 (en) * | 1999-02-25 | 2001-03-22 | Ulrich Hollmann | Decorative wall, ceiling or facade coating with a structured, roughened surface and process for their production |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5225134A (en) * | 1991-02-08 | 1993-07-06 | Concrete Design Specialties, Inc. | Methods of forming contoured walls |
GB9219867D0 (en) * | 1992-09-21 | 1992-10-28 | Baker Colin A | Method and tool for constructing a wall |
US5447752A (en) * | 1993-01-08 | 1995-09-05 | Cobb; Clyde T. | Method for making a decorative cementitous pattern on a surface |
US5395442A (en) * | 1993-04-14 | 1995-03-07 | Boral Concrete Products, Inc. | Lightweight concrete roof tiles |
US5904886A (en) * | 1995-07-21 | 1999-05-18 | Surface Technologies | Process for making a multi-layered decorative article |
US6403004B1 (en) | 1995-07-21 | 2002-06-11 | Surface Technologies, Inc. | Process for making a multi-layered solid surface article |
IL122201A0 (en) * | 1997-11-16 | 1998-04-05 | Sharon Michael | Attached decorative stones |
GB0125392D0 (en) * | 2001-10-23 | 2001-12-12 | Glasslam Europ Ltd | Decorative panels and methods of manufacturing the same |
CA2689284C (en) * | 2007-05-29 | 2012-10-09 | Silong Guo | A method of making a pattern on a building on site |
ES2299410B1 (en) * | 2007-10-30 | 2009-08-03 | Pedro Puig Gonzalez | STRIPS TO FIT CEMENT, MORTAR OR PLASTER. |
JP5348921B2 (en) * | 2008-03-31 | 2013-11-20 | ニチハ株式会社 | Manufacturing method of wood cement board |
JP5548340B2 (en) * | 2008-03-31 | 2014-07-16 | ニチハ株式会社 | Manufacturing method of wood cement board |
CN101509314B (en) * | 2009-03-12 | 2013-10-02 | 上海墙特节能材料有限公司 | Wall face brick mold and method for making cast in suit wall face brick using the mold |
US10221527B2 (en) * | 2014-07-28 | 2019-03-05 | W. Robert Wilson | Dry polymer cement overlay for trafficked pavements |
KR102600749B1 (en) * | 2021-09-24 | 2023-11-09 | 울산과학기술원 | Microfluidic module and method for fabricating the microfluidic module |
KR102558147B1 (en) * | 2021-09-24 | 2023-07-20 | 울산과학기술원 | Microfluidic film and method for fabricating the microfluidic film |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2059520A (en) * | 1936-11-03 | Building material and process of | ||
US1532684A (en) * | 1923-07-09 | 1925-04-07 | William A Carter | Method of facing wall structures |
US1564578A (en) * | 1924-10-15 | 1925-12-08 | Henry G Kennedy | Pattern for marking walls and method of using same |
US1571849A (en) * | 1925-06-25 | 1926-02-02 | Edward A Long | Method of making building blocks |
US2355967A (en) * | 1943-10-29 | 1944-08-15 | Marion E Greenwalt | Concrete block mold |
GB649808A (en) * | 1948-12-04 | 1951-01-31 | Dunlop Rubber Co | Improvements in or relating to the manufacture of articles of or containing rubber |
US2964800A (en) * | 1955-08-24 | 1960-12-20 | Dorsett Roscoe | Manufacture of a wall |
US3096195A (en) * | 1960-04-11 | 1963-07-02 | David C Seman | Process for producing an ornamental wall facing |
US3318563A (en) * | 1964-07-08 | 1967-05-09 | George G Downing | Concrete block mold assembly |
GB1376895A (en) * | 1970-12-10 | 1974-12-11 | Banbury Buildings Holdings Ltd | Simulated brick article of concrete or like material |
JPS5131261B1 (en) * | 1971-02-26 | 1976-09-06 | ||
US4002713A (en) * | 1972-04-13 | 1977-01-11 | Imperial Chemical Industries Limited | Cementing compositions and concretes and mortars derived therefrom |
US4217379A (en) * | 1976-07-06 | 1980-08-12 | Salvador Silvano E | Method for creating a simulated brick surface or the like |
JPS5477418A (en) * | 1977-11-17 | 1979-06-20 | Umehiko Kk | Method of figuring solid pattern to surface of construction portion material |
US4670208A (en) * | 1980-08-14 | 1987-06-02 | Peter Koblischek | Method of manufacturing machine supports by means of concrete polymer |
EP0069586B1 (en) * | 1981-07-07 | 1986-04-02 | Marley Tile AG | Polymer-modified cement mortars and concretes and processes for the production thereof |
JPS60233264A (en) * | 1984-05-02 | 1985-11-19 | 長田 秀晴 | Formation of embossed pattern |
US4746365A (en) * | 1985-02-19 | 1988-05-24 | Construction Products Research, Inc. | Utilization of latexes with hydraulic cement and gypsum compositions |
JPS62111062A (en) * | 1985-11-07 | 1987-05-22 | 長田 秀晴 | Surface finish of building or base material thereof |
US4968734A (en) * | 1986-07-01 | 1990-11-06 | W. R. Grace & Co.-Conn. | Cement admixture |
US4792360A (en) * | 1987-06-30 | 1988-12-20 | The Dow Chemical Company | Workable cement composition of low water content containing a hydroxyalkyl (meth)acrylate polymer |
US4851456A (en) * | 1988-02-03 | 1989-07-25 | Neverwear Corporation | Topcoat composition and method |
GB2214858A (en) * | 1988-02-10 | 1989-09-13 | John Garrett | Method of producing a decorative surface finish |
US4952104A (en) * | 1988-04-27 | 1990-08-28 | Hideharu Osada | Method of finishing the surface of a structure |
US5041475A (en) * | 1989-04-19 | 1991-08-20 | Osaka Yuki Kagaku Kogyo Kabushiki Kaisha | Method for production of inclusion water for hardening gypsum, method for production of shaped article of gypsum, and shaped article of gypsum |
-
1991
- 1991-02-07 US US07/651,950 patent/US5169573A/en not_active Expired - Fee Related
- 1991-02-08 DE DE69106731T patent/DE69106731T2/en not_active Expired - Fee Related
- 1991-02-08 DK DK91101761.4T patent/DK0441391T3/en active
- 1991-02-08 NO NO910509A patent/NO179419C/en not_active IP Right Cessation
- 1991-02-08 EP EP91101761A patent/EP0441391B1/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19908235C2 (en) * | 1999-02-25 | 2001-03-22 | Ulrich Hollmann | Decorative wall, ceiling or facade coating with a structured, roughened surface and process for their production |
Also Published As
Publication number | Publication date |
---|---|
NO179419C (en) | 1996-10-02 |
DK0441391T3 (en) | 1995-05-29 |
NO910509D0 (en) | 1991-02-08 |
NO179419B (en) | 1996-06-24 |
EP0441391A2 (en) | 1991-08-14 |
DE69106731T2 (en) | 1995-06-29 |
NO910509L (en) | 1991-08-12 |
US5169573A (en) | 1992-12-08 |
DE69106731D1 (en) | 1995-03-02 |
EP0441391A3 (en) | 1992-08-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0441391B1 (en) | Method of forming three dimensional patterns | |
AU679367B2 (en) | Grid for producing a pattern on a surface | |
US20020064637A1 (en) | Coated concrete surface and a process for coating a concrete surface | |
EP0422340A1 (en) | Panel for applying to a building and method for producing the same | |
JP2790354B2 (en) | Three-dimensional pattern forming method | |
JPH04169657A (en) | Solid pattern formwork and solid pattern forming method using same formwork | |
KR102187159B1 (en) | Slip-resistant non-slip composition using cement mixture and slip-resistant construction method using it | |
WO2000007831A1 (en) | Method of transferring matters to be displayed including designs, patterns and characters | |
JP2623662B2 (en) | Repair method of concrete structure | |
JP4395126B2 (en) | Paving method | |
JP4395125B2 (en) | Paving method | |
JPH0752875Y2 (en) | Form removal jig | |
JP4372071B2 (en) | Paving method | |
JP4118090B2 (en) | Surface treatment method for pavement | |
JP2622921B2 (en) | Paving method and paving material | |
TW299383B (en) | The construction method for concrete tile with paper-mold | |
JPH04131406A (en) | Method for forming solid patterns | |
JP2967853B2 (en) | Colored concrete construction method | |
KR100477757B1 (en) | A construction method for packing concrete protected layer by ceramic materials | |
JP2945982B2 (en) | Wall painting method | |
JPH05311843A (en) | Formation of color tile covering | |
JP2849261B2 (en) | Waterproof pavement method for steel deck | |
JP2000129613A (en) | Surface treatment of pavement | |
JPH02171465A (en) | Nonslip formation for coated floor face consisting of acrylic resin concrete | |
JP2011140871A (en) | Braille paving tile for visually handicapped person |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE |
|
17P | Request for examination filed |
Effective date: 19921104 |
|
17Q | First examination report despatched |
Effective date: 19930809 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): DE DK FR GB IT NL SE |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE DK FR GB IT NL SE |
|
ITF | It: translation for a ep patent filed | ||
REF | Corresponds to: |
Ref document number: 69106731 Country of ref document: DE Date of ref document: 19950302 |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: FR Ref legal event code: CD |
|
NLT1 | Nl: modifications of names registered in virtue of documents presented to the patent office pursuant to art. 16 a, paragraph 1 |
Owner name: MITSUI CHEMICALS, INC. |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20020206 Year of fee payment: 12 Ref country code: GB Payment date: 20020206 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20020212 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DK Payment date: 20020213 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20020227 Year of fee payment: 12 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20020228 Year of fee payment: 12 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030208 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030209 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030902 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
EUG | Se: european patent has lapsed | ||
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20031031 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20030901 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050208 |